Scalable multifunctional MOFs-textiles via diazonium chemistry

Cellulose fiber-based textiles are ubiquitous in daily life for their processability, biodegradability, and outstanding flexibility. Integrating cellulose textiles with functional coating materials can unlock their potential functionalities to engage diverse applications. Metal-organic frameworks (MOFs) are ideal candidate materials for such integration, thanks to their unique merits, such as large specific surface area, tunable pore size, and species diversity. However, achieving scalable fabrication of MOFs-textiles with high mechanical durability remains challenging. Here, we report a facile and scalable strategy for direct MOF growth on cotton fibers grafted via the diazonium chemistry. The as-prepared ZIF-67-Cotton textile (ZIF-67-CT) exhibits excellent ultraviolet (UV) resistance and organic contamination degradation via the peroxymonosulfate activation. The ZIF-67-CT is also used to encapsulate essential oils such as carvacrol to enable antibacterial activity against E. coli and S. aureus. Additionally, by directly tethering a hydrophobic molecular layer onto the MOF-coated surface, superhydrophobic ZIF-67-CT is achieved with excellent self-cleaning, antifouling, and oil-water separation performances. More importantly, the reported strategy is generic and applicable to other MOFs and cellulose fiber-based materials, and various large-scale multi-functional MOFs-textiles can be successfully manufactured, resulting in vast applications in wastewater purification, fragrance industry, and outdoor gears.

4. The EPR signal for OH radicals is too small to be visible.It may not be the dominant contributor to dye degradation.The continuous degradation of dye by ZIF-67 is remarkable (Fig. S21).A related work about using MOF/fiber as the catalyst for organic compound continuous degradation by the Farha group could be cited for comparison (doi:10.1002/adma.202300951) 5. ZIF-67-CT and ZIF-67-CT/Carvacrol seems decolored from purple in the inoculation with (i) E. coli and (j) S. aureus and incubation for 24 h.Could the authors explain the reason?Carvacrol loading in the composite should be studied.

Reviewer #3 (Remarks to the Author):
In this study, the authors report on a facile and scalable approach for directly integrating ZIF-67 (mainly) and ZIF-8 onto cotton fibers subjected to grafting through diazonium chemistry.The ZIF-67-Cotton textile (ZIF-67-CT) shows various features, including ultraviolet (UV) resistance characteristics, contamination degradation (via peroxymonosulfate activation), self-cleaning, antifouling, and oil-water separation.However, the reviewer believes that the novelty of this work is absent, including but not limited to preparing carboxymethylated cotton fabric to facilitate an in situ growth of metal-organic frameworks (MOFs) on them, which was already demonstrated in the previous report (Li et al., ACS Nano 2022, 16, 14779−14791) from the same research group.The only difference between the previous report (Li et al., ACS Nano 2022, 16, 14779−14791) and this manuscript in preparing the composite material is whether metal-containing and ligand-containing precursor solutions are separated.Furthermore, such methods for integrating MOFs into fiber substrates have already been extensively studied.Assessing the novelty of the research and the integrity of the experimental results, I, as a reviewer, do NOT recommend that this paper be published in Nature Communications.
Herein, I put several suggestions and questions regarding the manuscript.I kindly request that the authors address these points and consider submitting this manuscript to other journals.
1. Please add the page number to the manuscript.
2. (Line 50-54 on page 2) Relevant references are absent concerning dip-coating, hot-pressing, and spraying methods for MOF integration, although those are stated in the text.
3. (Line 54-57 on page 2) It seems that the authors claim that the references (#30-#34) only demonstrate the physical incorporation of MOFs into polymeric fiber substrates, but it is not… The key to some of the work the authors of this work refer to is associated with the chemical integration of MOFs into textiles.Please double-check the references and replace them (not related) with relevant ones.
4. (on page 3) It is stated that "In addition, the fabrication of ZIF-67-CT is facile and scalable…" According to the preparation methods of MOF-textiles in this work, it takes more than a day, including a carboxymethylation of cotton fabric and MOF growth onto it.A more detailed explanation regarding the extent of being "facile and scalable" compared to other reported MOFs-textiles is necessary to convince the reviewers and readers.
5. (Line 99-101 on page 4) It is stated that "Scanning electron microscopy (SEM) micrographs show that lots of ZIF-67 particles are evenly distributed on the carboxymethylated fiber surface, forming a MOF coating (Fig. 2c)."The resolution of the SEM image (Fig. 2c, right) is not good enough to tell the morphology of ZIF-67 on the fiber surface.Taking a higher magnification image of the sample is recommended.In addition, Fig. S6 and S7 do not agree with the text.Please revise it.
6. (Line 116-117 on page 4) The authors claim that "as observed in Fig. 2e, the results from XPS indicate the presence of carbon, oxygen, nitrogen and cobalt species in ZIF-67-CT, which are well in agreement with EDS results."In this work, the authors have only considered the presence of the major elements comprising ZIF-67.However, it is recommended that the authors maximize the utilization of the obtained XPS data by calculating element area ratios from XPS for comparison with those of ZIF-67 synthesized in the liquid phase.
7. (Line 121-125 on page 5) The authors claim that "The fabricated ZIF-67-CT 121 and ZIF-67 have the same crystal characteristic peaks, consistent well with the simulated crystal pattern of ZIF-67…" As shown in Fig. 2g (on page 6), It appears that there are shifts in the major peaks corresponding to ZIF-67 among ZIF-67-CT, ZIF-67 powder, and simulated ZIF-67.In addition, it is highly recommended that the authors calculate the specific values of the lattice parameters, peak broadness, and peak intensity ratios of the ZIF-67 component on the fabric to investigate any structural differences compared to freestanding ZIF-67 crystal powder.
8. (Line 157-159 on page 7) The authors state that "the modified ZIF-67-CT exhibits excellent superhydrophobic and superoleophilic properties and shows good acid and alkali resistance stability (Supplementary Fig. S15)."Time-dependent chemical stability data for modified ZIF-67-CT should be conducted and included in this work to claim the point above.9. (Line 170-172 on page 7) The authors mention that"…which may be due to the transition of electrons [36] of the Co2 + of ZIF-67."More detailed but concise information regarding the speculation is required to be included.10. (Line 221-223 on page 9) The authors claim that "… the ZIF-67-CT exhibits superior antibacterial activity against bacteria…" I understand that the ZIF-67-CT shows antibacterial activity through the data provided in the manuscript.Still, as a reader, I cannot tell how effective the ZIF-67-CT is in comparison with other MOF-textile samples and related materials.Please make a good comparison with other materials in the antibacterial activity.
11. (Line 230-232 on page 9) The authors claim that "… the ZIF-67-CT exhibited excellent catalytic performance."I cannot find any dye degradation kinetic data (dye concentration vs. time) in the main text as well as in the supplementary document.Please provide the kinetic data.
12. (Line 245-247 on page 10) The authors claim that "The SEM images of the ZIF-67-CT after washing show the same morphology structure as before washing…" However, there appears to be a noticeable change before and after the fabric composite washing (Fig. 4e).It is recommended that the authors take SEM images of the washed samples at varied locations.I do not think the SEM images in Fig. S24 represent the samples after washing.13. (Line 250-252 on page 10) The authors state that "… the fiber structure damage of ZIF-67-CT during the modification processes…" Here, the authors should characterize CT-COOH and ZIF-67-CT after washing to confirm what causes the fiber structure damage of ZIF-67-CT, and to identify the relationship between fiber treatment methods and fiber mechanical properties.
14. (Line 255-257 on page 10) The authors claim that "These results demonstrate no obvious change in physical-mechanical properties, which does not affect its daily use."In order to claim that point, the authors should show N2 isotherms of ZIF-67-CT after washing and compare with those of as-prepared ZIF-67-CT.Surface area, pore volume, and porosity are closely related to MOF-textiles properties, so maintaining such properties after laundering stability tests is critical in this work.
15. (Line 307-309 on page 13) The authors conclude that "Besides ZIF-67 MOF and cotton textiles, our developed strategy can also be applied to other MOFs (for example, ZIF-8 MOF)…" In my humble opinion, demonstrating ZIF-8 integration is not enough to claim the method is generic.The authors need to show other MOFs beyond the ZIFs with SOD (sodalite-like) structures.

Point-by-Point Responses to Referees' Comments
We thank all the referees for their in-depth review of our manuscript and for enriching us with their valuable comments and suggestions, which have helped us further improve the quality of the manuscript.The referees' comments are listed in blue font color, and the authors' responses are listed in black font color.All the changes in the revised manuscript and supplementary information are marked in red font color.

Referee #1:
Li et al report developed a scabble synthesis ZIF-67 coated cotton textile.The synthesis and performance are detailed studied.It is a good sample for the field of MOF functionalized composite and the applications are interesting.It could be published after fixing the concern.

Response:
We really appreciate your in-depth review of our manuscript.According to your comments and suggestions, we have revised and improved our manuscript.
Other comments: 1.Several other papers about ZIF-67 coating on textiles should be cited and compared.The current method shows advancement compared with other ZIF-67 coatings, so getting other ZIF-67 coating work involved in the performance factors study (Figure 1 b) is suggested.

Response:
We thank the referee for the valuable comment.As shown in Fig. 1b (revised), we have added and compared with other ZIF-67 coating works regarding various key performance factors: scalability, mechanical stability, porosity, fragrance encapsulation, pollutant degradation, and antibacterial activity.As a result, our method shows great advancement in scalability, fragrance encapsulation, and antibacterial activity (Supplementary Note 1). 2. The sample after washing seems slightly faded, so the residual MOF content after washing testing should be numerically reported.The authors stated that washed ZIF-67 MOF coating structure was well maintained by SEM (Supplementary Fig. S24) and XRD (Supplementary Fig. S25), but the samples are marked as ZIF-8 in captions.The porosity (by N2 sorption) of the washed sample should be added.

Response:
We thank the referee for the valuable comment.We are very sorry for our mistake about the wrong captions of ZIF-8, which have been corrected to be ZIF-67-CT in Supplementary Fig. S27 (SEM) and Supplementary Fig. S28 (XRD).In addition, we have added the N2 adsorption-desorption isotherm BET of the washed sample in Supplementary Fig. S29.The BET surface area is 207.6 m² g -1 , and the pore width of the mesoporous structure is mainly at ≈ 0.64 nm.The reason for the BET decrease of the washed sample is mainly due to the loss of MOF during the laundering process.
Hence, the residual MOF content after the washing testing is calculated to be ∼ 10.6% based on the changes in BET surface area (the MOF content before the washing testing is ∼ 12.7%).
3. The ZIF-67 coating content on cotton seems not correct from the TGA analysis.The residual after calcining is oxides, not ZIF-67.The wrong method will underestimate the MOF content.If the ZIF-69 content is 3.92%, the BET surface area increase from coating component contribution is 5600m2/g.Obviously, it is impossible for ZIF-67.A loading study by ICP-OES test and normalized BET surface area calculation are suggested to understand the coating quality (doi:10.1021/accountsmr.2c00200)

Response:
We thank the referee for the valuable comment.As suggested by the referee, we have added the normalized BET surface area calculation to test the MOF coating content of ZIF-67-CT.As shown in Fig. 2h and Supplementary Fig. S10, the BET surface area of CT, ZIF-67-CT, and ZIF-67 particles is 21.6, 244.2, and 1750.4 m² g -1 , respectively.So, the ZIF-67 coating content of ZIF-67-CT is measured to be 12.7%, according to the normalized BET surface area calculation [45].
We also thank the referee for providing this valuable reference for us to understand the coating quality.This reference has been included in the revised manuscript as ref [45].

The EPR signal for OH radicals is too small to be visible. It may not be the dominant contributor to dye degradation. The continuous degradation of dye by ZIF-67 is remarkable (Fig. S21).
A related work about using MOF/fiber as the catalyst for organic compound continuous degradation by the Farha group could be cited for comparison (doi:10.1002/adma.202300951)

Response:
We are really grateful for this comment.We have rechecked the EPR test results of ZIF-67-CT and corrected the signal marked of OH and SO4 -radicals in the revised Fig. 4d.As mentioned by the referee, the signal of OH radicals is significantly stronger than SO4 -radicals.Therefore, the SO4 - radical is not the dominant contributor to the dye degradation, but the OH radical is.In addition, as one comparison reference, the published work (10.1002/adma.202300951) has been cited in the revised manuscript as ref [11].

ZIF-67-CT and ZIF-67-CT/Carvacrol seems decolored from purple in the inoculation with (i) E. coli and (j) S. aureus and incubation for 24 h. Could the authors explain the reason?
Carvacrol loading in the composite should be studied.

Response:
We thank the referee for the valuable comment.Indeed, ZIF-67-CT and ZIF-67-CT/Carvacrol are decolored in the inoculation with (i) E. coli and (j) S. aureus and incubation for 24 h.However, ZIF-67-CT and ZIF-67-CT/Carvacrol would not be decolored in the air for a long time (for example, 180 days).Therefore, this phenomenon is mainly due to the fact that Co ions of ZIF-67 would gradually release when incubated in an LB solid medium with bacterial suspension.Importantly, the released Co ions would contact and interact with the proteins and nucleic acids of the bacterial membrane, damaging the bacterial membrane and cell wall, and then leading to bacterial destruction and death, which is the dominant reason for ZIF-67-CT to enable antibacterial activity.This phenomenon and antibacterial performance can be further explained by ref [R3].
As suggested by the referee, we have added the Carvacrol loading in the composite calculated by the gravimetric method.Owing to the large surface area and porosity of ZIF-67, the Carvacrol loading content of ZIF-67-CT was up to about 90 mg g −1 , whereas the pristine CT was only about 3 mg g −1 .

Referee #3:
In this study, the authors report on a facile and scalable approach for directly integrating ZIF-67 (mainly) and ZIF-8 onto cotton fibers subjected to grafting through diazonium chemistry.The ZIF-67-Cotton textile (ZIF-67-CT) shows various features, including ultraviolet (UV) resistance characteristics, contamination degradation (via peroxymonosulfate activation), self-cleaning, antifouling, and oil-water separation.However, the reviewer believes that the novelty of this work is absent, including but not limited to preparing carboxymethylated cotton fabric to facilitate an in situ growth of metal-organic frameworks (MOFs) on them, which was already demonstrated in the previous report (Li et

Response:
We appreciate the efforts and time that Referee #2 has devoted to assess our manuscript and provide very valuable and insightful comments.According to your comments and suggestions, we have revised and improved our manuscript.
Firstly, it appears that our manuscript's main dimensions of novelty were not well presented and fully identified.Therefore, we would like to use this response to re-highlight our novelty and share our thoughts about those points that might need our clarification.In our work, we demonstrate a generic strategy for preparing highly stable, large-scale, multifunctional MOFs-textiles via diazonium chemistry.The two facile steps are readily accomplished via diazonium chemistry and in situ growth successively by soaking a cotton textile in 3-aminobenzoic acid diazonium salt HCl solution and metal-contenting and ligand-contenting solution, respectively.Specifically, the covalent grafted carboxyl polymer chain brushes on the fiber surface create abundant carboxyl group sites, which assist the initial coordination of cobalt ions to the fiber surface at the molecular level and facilitate the subsequent in situ growth of MOF nanoparticles, forming a uniform and dense MOFs coating.This strategy is expected to provide a new avenue for fabricating scalable multifunctional MOFs-textiles.
Secondly, regarding the comment "preparing carboxymethylated cotton fabric to facilitate an in situ growth of metal-organic frameworks (MOFs) on them, which was already demonstrated in the previous report (Li et  ), the main research contents are focused on the morphology changes with the reaction conditions (Layer-by-Layer cycles and water content percentage), the water stability of CuBTC coating, anti-icing performance and its anti-icing mechanism with COMSOL simulation.However, our work is unique and more in-depth, as it offers a generic strategy for preparing highly stable, large-scale, multifunctional MOFs-textiles, which is applicable to various types of MOFs (for example, ZIF-8, UiO-66-NH2, and MOF-303) and different cellulose-based fibers (for example, linen and paper).
Thirdly, regarding the comment "Furthermore, such methods for integrating MOFs into fiber substrates have already been extensively studied."Indeed, the field of metal-organic frameworks (MOFs) has seen tremendous growth in the past two decades, with extensive research focused on tuning MOF chemistry and pore structures for specific applications [R4-R6].Most studies have examined MOFs in their powder form, while reports of the integration of MOFs into alternative forms are much fewer.MOFs with large specific surface area, tunable pore size, and excellent thermal and chemical stability, have been considerably applied to fabricate MOF/cellulose fiber composites [R7].And we agree with the referee that several methods for integrating MOFs into fiber substrates have already been studied in recent years [R8-R10].However, to the best of our knowledge, there are no reported methods that could be used to fabricate scalable MOF-Textiles (for example, tens meters long or larger than 7.5 m 2 as reported in our work), or generic and applicable to many types of MOFs (for example, ZIF-67, ZIF-8, UiO-66-NH2, and MOF-303).More importantly, in our work, the fabricated ZIF-67-CT endows the traditional textiles with more unique functions, which would broaden application prospects in the textile industry to improve the high added value of textiles, such as fragrance encapsulation, antibacterial, anti-fouling, oil-water separation, and wastewater purification.
Lastly, we would like to thank the referee for the valuable and insightful comments on our demonstrations.Indeed, combining this method's generality and scalability makes the industrial production of multifunctional MOF fabrics possible, leading to broad applications in the textile industry and our daily lives.
As such, we would like to highlight the key advances that we have made in this work:  Such a method enabled the scalable manufacturing of functional MOFs-textiles with high durability.A roll of ZIF-67-CT textile (0.25 m wide and 30 m long) was produced.
 The covalent bonding between ZIF-67 and carboxyl chains of cellulose fibers endowed this ZIF-67-textile highly stable in air and water.After laundering based on the international standard ISO 105 C10, no obvious changes in color and crystal structure or decreased integrity of the ZIF-67-textile were observed.
 The prepared MOFs-textiles offered excellent UV resistance, antibacterial, fragrance encapsulation (for example, Carvacrol), and wastewater purification (for example, MB, RhB, and MO dye solution).For example, the UPF was up to 71 higher than 50, and the antibacterial efficiency against E. coli and S. aureus was 99.99%, showing great potential in household products and industrial use.
 The as-prepared superhydrophobic MOFs-textiles would be widely used in outdoor products and public facilities with self-cleaning, antifouling, anti-icing, and oil-water separation properties.The total frozen time of superhydrophobic ZIF-67-CT was delayed from 90.5 s to 223.7 s, and the separation efficiency was up to 98.6% and still maintained above 97% after 15 cycles of the separation process.
 The fabrication of ZIF-67-CT is facile and scalable, and can also be applied to other cellulose-based fibers (for example, linen and paper) and MOFs (for example, ZIF-67, ZIF-8, UiO-66-NH2, and MOF-303), hence more valuable functions would be enabled for the practical applications of textiles, including improved environmental remediation, public health, and personal protective gears.Here are some major changes that we have made to substantially advance the manuscript:

R4. DeCoste
1) We have re-organized the introduction to clarify the main dimensions of novelty and to make a clear description about the generic and scalable strategy by the diazonium chemistry covalent graft modification technology.2) We have re-organized Fig. 1  Ref [30] shows that nonwoven fiber mats were coated with Al2O3 by atomic layer deposition (ALD) using a homemade hot-wall viscous-flow vacuum reactor, followed by layer-by-layer MOF growth (Atomic layer deposition coating).
Ref [31] shows that MOF-808 growth on fiber is via a three-stage process: (1) aggregation of an amorphous coordination polymer on the fibrous surface (0-10 min), ( 2) formation of MOF-808 nucleation sites (10-20 min), and (3) growth into a continuous MOF coating (>30 min).It is inferred that this period served as a pseudotemplating period during which reagents were adsorbed on the surface of the fiber and quickly formed an amorphous coordination polymer (Adsorption aggregation on the fiber surface).
Ref [33] shows that the synthetic procedure of MOF-808/PEI/fiber composite by being immersed into the suspension for 10 min, and then taken out from suspension.The wet fabric with 200% liquid pick-up was carefully put on an aluminium foil and dried in a hood overnight.(Impregnation method).
Ref [34] shows that the nanofibrous metal−organic framework filters were prepared by electrospinning with the mixture of MOFs and PAN (Mixing method).These mentioned references do not have a chemical covalent bond force between fibers and the MOF coating.We deleted ref [30], as it is similar to ref [32].The relevant references have been reorganized to be refs [29][30][31][32], due to the re-written introduction of the revised manuscript.

(on page 3) It is stated that "In addition, the fabrication of ZIF-67-CT is facile and scalable…"
According to the preparation methods of MOF-textiles in this work, it takes more than a day, including a carboxymethylation of cotton fabric and MOF growth onto it.A more detailed explanation regarding the extent of being "facile and scalable" compared to other reported MOFstextiles is necessary to convince the reviewers and readers.

Response:
We thank the referee for the valuable comment.The preparation of each type of MOF takes a certain amount of time to confirm its special crystal structures, for example, ZIFs MOF need more than 12 hours, supported by the following references [R11-R14].

Processing condition and time Reference
Room temperature for 15 h R11

Room temperature for 12 h R14
In our work, the carboxymethylation of cotton fabric is modified via diazonium radical graft polymerization, which can be completed from 1 to 24 h, and the grafting process time of more than 2 h is sufficient for the subsequent MOF growth.For example, the scalable textile sample shown in Fig. 5c was prepared within 3 h.More importantly, the whole manufacturing process can be finished at room temperature, which does not need high temperature, complex fabrication process, or special equipment, just one container (Fig. 5b).For example, a roll of ZIF-67-CT cloth (0.25 m wide and 30 m long) was easily produced using a container (diameter of 27 cm and height of 15 cm) in laboratory (Fig. 5c).Therefore, we stated "the fabrication of ZIF-67-CT is facile and scalable…".

(Line 99-101 on page 4) It is stated that "Scanning electron microscopy (SEM) micrographs
show that lots of ZIF-67 particles are evenly distributed on the carboxymethylated fiber surface, forming a MOF coating (Fig. 2c)."The resolution of the SEM image (Fig. 2c, right) is not good enough to tell the morphology of ZIF-67 on the fiber surface.Taking a higher magnification image of the sample is recommended.In addition, Fig. S6 and S7 do not agree with the text.Please revise it.

Response:
We thank the referee for the valuable comment.As suggested by the referee, we have replaced Fig. 2c (right) with a higher magnification SEM image to exhibit the morphology of ZIF-67 on the fiber surface.In addition, we are very sorry for our mistake about Figs.S6 and S7, and we have corrected the corresponding text in the revised manuscript.

(Line 116-117 on page 4)
The authors claim that "as observed in Fig. 2e, the results from XPS indicate the presence of carbon, oxygen, nitrogen and cobalt species in ZIF-67-CT, which are well in agreement with EDS results."In this work, the authors have only considered the presence of the major elements comprising ZIF-67.However, it is recommended that the authors maximize the utilization of the obtained XPS data by calculating element area ratios from XPS for comparison with those of ZIF-67 synthesized in the liquid phase.

Response:
We thank the referee for the valuable comment.As suggested by the referee, we have calculated the element atomic (%) and area ratios of ZIF-67-CT and ZIF-67 from the XPS test reports (Table R1).

(Line 121-125 on page 5)
The authors claim that "The fabricated ZIF-67-CT 121 and ZIF-67 have the same crystal characteristic peaks, consistent well with the simulated crystal pattern of ZIF-67…" As shown in Fig. 2g (on page 6), It appears that there are shifts in the major peaks corresponding to ZIF-67 among ZIF-67-CT, ZIF-67 powder, and simulated ZIF-67.In addition, it is highly recommended that the authors calculate the specific values of the lattice parameters, peak broadness, and peak intensity ratios of the ZIF-67 component on the fabric to investigate any structural differences compared to freestanding ZIF-67 crystal powder.

Response:
We thank the referee for the valuable comment.As shown in Fig. 2g, the characteristic peaks of ZIF-67 appear in the XRD patterns of ZIF-67-CT and ZIF-67 powder, which are the same as ZIF-67 simulated, indicating the successful synthesis of ZIF-67 crystal in this work.The slight shift in the major peaks is mainly caused by the difference in the sample state during the test processing.As known, the sample status, sample preferential orientation, and testing instrument model would affect the peak shift (for example, Angew.Chem.Int.Ed. 2016, 55, 3419-3423).
As for the comment "In addition, it is highly recommended that the authors calculate the specific values of the lattice parameters, peak broadness, and peak intensity ratios of the ZIF-67 component on the fabric to investigate any structural differences compared to freestanding ZIF-67 crystal powder."As shown in Fig. R1, the ZIF-67-CT has the crystal characteristic peaks of ZIF-67 at the same 2 theta positions with freestanding ZIF-67 powder, which demonstrated that the ZIF-67 component on the fabric and freestanding ZIF-67 powder has same lattice parameters.However, the main difference between the ZIF-67 component on the fabric and freestanding ZIF-67 powder is peak broadness and peak intensity, which represent the content of the ZIF-67 crystal structure in the tested samples.The freestanding ZIF-67 powder has 100% of ZIF-67 crystal, whereas the ZIF-67 crystal content of ZIF-67-CT is measured to be 12.7%, according to the normalized BET surface area calculation.Therefore, the intensity of freestanding ZIF-67 crystal powder is higher than ZIF-67-CT.As shown in Table R2, the peak width at half height of ZIF-67-CT and ZIF-67 crystal powder is 0.257 and 0.265, respectively.And the peak intensity ratio of ZIF-67 component on the fabric and freestanding ZIF-67 crystal powder is 0.2865 at the main peak (2 Theta=7.2) in Table R2.
In addition, the BET is the main method to identify the micropores and specific surface area of MOFs.Moreover, we combined the ATR-FTIR, XPS, and SEM tests to confirm the structures of MOFs.Thus, we believe these results are sufficient to support our claims regarding the prepared ZIF-67-CT with great ZIF-67 crystal structures in this work.Besides, other published papers about ZIF-67 or other MOFs@fiber composites can support our conclusion, as

Response:
We thank the referee for the valuable comment.As suggested by the referee, we have added the time-dependent chemical stability test data.As shown in Supplementary Fig. S16, the ZIF-67-CT was sunk to the bottom of the acid and alkali solutions (Figs.S16a and S16c, left), and the color of ZIF-67-CT was transformed from purple into a faint yellow after soaking for 48 h at 30 °C.On the contrary, the modified superhydrophobic ZIF-67-CT completely floated on the water in the bottle (Figs.S16a and S16c, right) due to the superhydrophobicity, and the color of the superhydrophobic ZIF-67-CT was not changed even after soaking under the same conditions.The ZIF-67 crystal structure of ZIF-67-CT was lost after soaking for 48 h (Figs.

(Line 170-172 on page 7)
The authors mention that"…which may be due to the transition of electrons [36] of the Co2+ of ZIF-67."More detailed but concise information regarding the speculation is required to be included.

Response:
We thank the referee for the valuable comment.We have added concise information about the ultraviolet mechanism in the revised manuscript, and the anti-ultraviolet mechanism of the ZIF-67-CT is explained as follows.Because metallic oxide is a good inorganic UV blocker, the UV absorption of MOF coating stems from the transition of electrons, which can be supported by the following references [R22 and R23].Specifically, when there is no external stimulus light, the electrons of metal in the MOF stay in the valence band of low energy.Once the ZIF-67 is irradiated by the incident light, it absorbs the UV photonic energy, enabling the transition of electrons from the valence band to the conduction band with high energy.

Response:
We are really grateful for this comment.As we stated in the manuscript "We calculated the antibacterial efficiency using the plate count method, and found the antibacterial efficiency of ZIF-67-CT and ZIF-67-CT/Carvacrol against E. coli and S. aureus was 99.99% (Supplementary Fig. S21)."When the antibacterial efficiency of one sample is above 90%, which can be defined as the sample with great antibacterial activity.In this work, the antibacterial efficiency of the prepared sample is up to 99.99%, showing superior antibacterial activity against E. coli and S. aureus.And this can be further compared with other refs [R24-R26].In addition, the inhibition zones of most MOFs are typically within 0.5-20.0mm, and the summary of the antibacterial action of selected MOFs can be found in ref [R27].While, the inhibition zone of our prepared ZIF-67-CT/Carvacrol inoculated E. coli is obviously increased to 33.0 mm, especially for S. aureus (90.0 mm), significantly larger than 20.0 mm (Supplementary Fig. S20).Therefore, combining the discdiffusion analytic method and plate count method results, the ZIF-67-CT exhibits superior antibacterial activity, especially the carvacrol-loaded ZIF-67-CT.
COOH are similar to CT, indicating that the carboxymethylation process would not influence its flexural rigidity and air permeability performances.In addition, compared to CT-COOH, the air permeability of ZIF-67-CT is decreased from 258.6 mm s -1 to 203.5 mm s -1 (Fig. 4h), attributed to the loaded MOF coating on the fiber surface of ZIF-67-CT.

Response:
We thank the referee for the valuable comment.We have added the N2 adsorption-desorption isotherm BET and the pore width distribution of the washed sample.As shown in Supplementary Fig. S29, the BET surface area of the washed sample is 207.6 m² g -1 , and the pore width of the mesoporous structure is mainly at ≈ 0.64 nm.Compared to ZIF-67-CT before laundering (244.2 m² g -1 ), the BET surface area is decreased by about 15%, mainly because some MOF particles are off the fiber surfaces during the laundering process.This result indicated that the laundering process

Fig. 5
Fig. 5 Scalable manufacturing of the ZIF-67-CT.a, The fabrication process of the ZIF-67-CT via in-situ growth.b, Photographs showing the fabrication process of ZIF-67-CT.c, Photographs of the large-scale ZIF-67-CT (30 m × 0.25 m).
S16b and S16d), whereas the characteristic peaks of the modified superhydrophobic ZIF-67-CT were well maintained.The timedependent chemical stability test data results demonstrate that the superhydrophobic modification of ZIF-67-CT shows good acid and alkali resistance stability.Supplementary Fig. S16 Photographs of ZIF-67-CT (left) and modified superhydrophobic ZIF-67-CT (right) after exposure to a pH=2 (a) and pH=13 (c) solution for 48 h at 30 °C.The corresponding XRD patterns of ZIF-67-CT and modified superhydrophobic ZIF-67-CT after exposure to a pH=2 (b) and pH=13 (d) solution.

These references about other ZIF-67 coating works have been included in the revised manuscript as refs [39] and [40]. Fig. 1b (revised) Comparison
of the performance factors of ZIF-67-CT to those of pristine, conventionally modified cotton textiles, and other ZIF-67 coating textiles.
by adding the compared performance factors offered by other ZIF-67 coating works.3)Wehavere-organized Fig.2cto replace the low magnification SEM image with a higher magnification SEM image to clearly exhibit the morphology of ZIF-67 on the fiber surface, method for preparing metal-organic-framework coatings.Angew Chem Int Ed 55, 3419-3423 (2016).35.Li C, Zhang Q, Sun J, Li T, E S, Zhu Z, et al.High-performance quasi-solid-state flexible aqueous rechargeable Ag-Zn battery based on metal-organic frameworkderived Ag nanowires.ACS Energy Letters 3, 2761-2768 (2018).
T, Chen Z, Li P, Wasson MC, Chen Y, et al.Scalable and template-free aqueous synthesis of zirconium-based metal-organic framework coating on textile fiber.J Am Chem Soc 141, 15626-15633 (2019).

Table R2 .
Peak width at half height and peak intensity of ZIF-67 component on the fabric and freestanding ZIF-67 crystal powder.
CT should be conducted and included in this work to claim the point above.
Thus, the ZIF-67-CT exhibits excellent UV protection performance.
R22. Shi YE, Zhuang X, Cao L, Gou S, Xiong Y, Lai WF, et al.Copper-Nanocluster-Based Transparent Ultraviolet-Shielding Polymer Films.ChemNanoMat 5, 110-115 (2019).R23.Li W, Liu K, Zhang Y, Guo S, Li Z, Tan SC.A facile strategy to prepare robust selfhealable superhydrophobic fabrics with self-cleaning, anti-icing, UV resistance, and antibacterial properties.Chem Eng J 446, 137195 (2022).10. (Line 221-223 on page 9) The authors claim that "… the ZIF-67-CT exhibits superior antibacterial activity against bacteria…" I understand that the ZIF-67-CT shows antibacterial activity through the data provided in the manuscript.Still, as a reader, I cannot tell how effective the ZIF-67-CT is in comparison with other MOF-textile samples and related materials.Please make a good comparison with other materials in the antibacterial activity.